US6645902B2 - Adsorbent having capability of decomposing organic halogen compounds and method for producing the same - Google Patents

Adsorbent having capability of decomposing organic halogen compounds and method for producing the same Download PDF

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US6645902B2
US6645902B2 US10/031,140 US3114002A US6645902B2 US 6645902 B2 US6645902 B2 US 6645902B2 US 3114002 A US3114002 A US 3114002A US 6645902 B2 US6645902 B2 US 6645902B2
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organic
catalyst
organic halogen
activated carbon
adsorbent
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US20020177524A1 (en
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Masakatsu Hiraoka
Katsuhiro Tokura
Kazuyuki Oshita
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Metawater Co Ltd
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NGK Insulators Ltd
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
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    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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    • B01J20/28078—Pore diameter
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    • B01J20/28088—Pore-size distribution
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/901—Activated carbon

Definitions

  • the present invention relates to adsorbents having the capability of decomposing organic halogen compounds and being adapted to be used mainly for treating waste gases from incinerators and also to a process for producing the same.
  • the temperature must be maintained at as high as 1000° C. or more for combustion processes to completely decompose chlorinated organic materials like organic halogen compounds through oxidation.
  • the combustion temperature is commonly set at 800 to 900° C., and therefore it is not easy to completely decompose the organic halogen compounds through oxidation by improving the combustion conditions.
  • dioxins and brominated dioxins are not only produced during a combustion process, but they are also synthesized again from remaining unburnt materials that are not completely burnt and precursor materials having benzene rings in a wide temperature ranges of about 300 to 500° C.
  • the organic halogen compounds such as dioxins and brominated dioxins may be synthesized again during the succeeding stage, so that the organic halogen compounds including dioxins and brominated dioxins may not be reduced in the waste gases.
  • the organic halogen compounds including dioxins and brominated dioxins are required to be reduced by treating the waste gases so that the organic halogen compounds may be stably maintained at a low concentration in the waste gases.
  • an adsorbing method by which such organic halogen compounds are adsorbed with activated carbon is mainly employed.
  • the activated carbon having adsorbed the organic halogen compounds becomes a secondary waste product, which requires post treatment thereof.
  • the present invention has been accomplished to solve the conventional problems as mentioned above, and to provide an adsorbent having the capability of decomposing organic halogen compounds.
  • the adsorbent not only adsorbs organic halogen compounds contained in waste gases, but also effectively decomposes them to prolong the life span of the adsorbent and to suppress the amount of a secondary waste produced, while having no ability to re-synthesize the organic halogen compounds (including dioxins and brominated dioxins) at that time.
  • the invention also provides a process for producing the same.
  • the adsorbent having the organic halogen compound-decomposing function according to the present invention which has been made to solve the above problems, comprises an activated carbon and an organic halogen compound-decomposing catalyst carried on the activated carbon.
  • the organic halogen compound-decomposing catalyst has fine particles of Pt and/or Pd dispersed in TiO 2 by mixing a dispersion liquid of an organic metal precursor containing Pt and/or Pd and Ti in molecules thereof with a sol of TiO 2 and producing the catalyst under heating.
  • a process for producing a catalyst having a capability of decomposing an organic halogen compound according to the present invention comprises the steps of reacting a salt of Pt and/or Pd, an organic titanium compound and an organic binder in a solvent, to thereby synthesize a dispersion of an organic metal compound precursor containing Pt and/or Pd and Ti in molecules thereof; mixing a sol of TiO 2 with the dispersion to prepare a catalyst-coating solution; impregnating an activated carbon with the catalyst-coating solution; and heating the resulting mixture, thereby allowing the activated carbon to carry thereon an organic halogen compound-decomposing catalyst comprising TiO 2 and, dispersed therein, fine particles of Pt and/or Pd.
  • the organic binder an amino acid such as L-lysine or L-proline is preferably used.
  • an alkoxide derivative of Ti is preferably used.
  • the adsorbent having the capability. of decomposing the organic halogen compound according to the present invention is produced through mixing the sol of TiO 2 with the dispersion of the organic metal compound precursor containing Pt and/or Pd and Ti in molecules thereof, followed by heating, thereby allowing the activated carbon to carry thereon the organic halogen compound-decomposing catalyst comprising TiO 2 having fine particles of Pt and/or Pd dispersed therein. Since the number of activated points is extremely large, that the catalyst can be highly activated. Therefore, while the amount of expensive Pt and Pd is reduced, the organic halogen compound can be decomposed.
  • the mixture of the organic metal compound precursor dispersion and the TiO 2 sol is heated at a temperature of approximately 450° C.-500° C. in an air atmosphere under ordinary atmospheric pressure.
  • the heating time is set at such a time in connection with the heating temperature, that the organic binder may be completely burnt out and that Pt and/or Pt may be uniformly dispersed in TiO 2 .
  • the organic halogen compound is not synthesized again, unlike the conventional V 2 O 5 —TiO 2 based catalyst or the V 2 O 5 —WO 3 —TiO 2 based catalyst.
  • the adsorbent exhibits an excellent function at the use temperature of the activated carbon of approximately 130-150° C., so that the useful life of the activated carbon can be prolonged to a few times longer than that of the conventional adsorbent, while the waste gases need not be re-heated.
  • FIG. 1 is a graph showing orthochlorotoluene-removing characteristics with activated carbons carrying Pt thereon.
  • FIG. 2 is a graph showing the concentration of orthochlorotoluene in adsorbents carrying Pt thereon.
  • FIG. 3 is a graph showing orthobromotoluene-removing characteristics with activated carbons carrying Pt thereon.
  • FIG. 4 is a graph showing the concentration of orthobromotoluene in adsorbents carrying Pt thereon.
  • FIG. 5 is a graph showing orthochlorotoluene-removing characteristics of activated carbons carrying Pd thereon.
  • FIG. 6 is a graph showing the concentration of orthochlorotoluene in adsorbents carrying Pd thereon.
  • FIG. 7 is a graph showing orthobromotoluene-removing characteristics with activated carbons carrying Pd thereon.
  • FIG. 8 is a graph showing the concentration of orthobromotoluene in adsorbents carrying Pd thereon.
  • a Ti alkoxide derivative used as an organic Ti compound for example, a derivative in which a part of a Ti alkoxide is replaced by an acetyl acetate group or a derivative in which a part of the Ti alkoxide is replaced by a triethanol aminate group
  • a soluble salt of Pt and/or Pd are dissolved into a solvent containing an organic binder.
  • soluble Pt salt chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, platinum tetrachloride, etc. may be used.
  • Pd salt palladium chloride, palladium nitrate, etc. may be used.
  • an amino acid such as L-lysine or L-proline may be used as the organic binder for Ti and the noble metal.
  • L-proline is preferred, because it has a high solubility in methanol to be used as a solvent.
  • the organic binder is a substance which bonds Ti ions and Pt and/or Pd ions with molecules of the organic binder, fixes them in the molecules and is removed by heating to produce bound fine particles of TiO 2 and Pt and/or Pd, while not affording adverse effects upon the physical properties, such as catalytic poison of the resulting organic halogen compound-decomposing catalyst.
  • the organic binder binds the Ti ions and the Pt and/or Pd ions, and fixes them in the molecules.
  • the mixing rates of the constituent ingredients are 100 wt. parts of the Ti alkoxide derivative, 0.5 to 5 wt. parts of the Pt and/or Pd salt, 100 to 200 wt. parts of methanol, and 0.1 to 1.5 wt. parts of the amino acid.
  • a dispersion of an organic metal compound precursor in which the above ingredients are uniformly dispersed in a molecular level is obtained.
  • the organic metal compound precursor means a compound in which Ti ions and Pt and/or Pd ions are bound inside one molecule via chemical bonds such that the ions have a fixed positional relationship that is different from a state in which the ions are dissolved in a solvent.
  • a catalyst-coating solution is obtained by mixing the dispersion with 50 wt. parts of a sol of Ti acting as a glue.
  • activated carbon is impregnated with the catalyst-coating solution and the resulting activated carbon is heated at 450 to 500° C., the amino acid organic binder is burnt out to decompose the organic metal compound precursor.
  • an adsorbent is provided having the capability of decomposing an organic halogen compound including the activated carbon on which is carried an organic halogen compound catalyst itself in which Pt and/or Pd are converted to super fine particles, which are highly dispersed in TiO 2 .
  • the activated carbon is preferably a granular activated carbon having particles of around approximately 3 mm-10 mm and a BET specific surface area of 300 m 2 /g or more.
  • TiO 2 fine particles having primary particle diameters of around 10 nm are dispersed in an acidic solution.
  • the TiO 2 sol contains around 30% of TiO 2 itself.
  • a solution of nitric acid or that of hydrochloric acid may be used. Considering the effect upon the activity of the catalyst itself, it is desirable to use a nitric acid solution of TiO 2 .
  • the above organic halogen compound-decomposing catalyst has improved catalytic activity, because the number of activated points is largely increased by the super fine particles of Pt and/or Pd. For this reason, the amount of expensive Pt and/or Pd used can be largely reduced as compared with the case where TiO 2 powder or sintered TiO 2 powder is coated or impregnated with an aqueous solution of a Pt and/or Pd salt and Pt and/or Pd is precipitated by thermal decomposition. Further, since the catalyst of the present invention has the capability to decompose the organic halogen compounds even at lower temperatures different from the conventional organic halogen compound-decomposing catalysts, the invention catalyst can exhibit excellent performance in a temperature range of approximately 130-150° C.
  • the waste gases need not be re-heated.
  • the organic halogen compounds can be decomposed without fear of re-synthesis of the organic halogen compounds such as dioxins or brominated dioxins.
  • heavy metals, SOx, NOx, HCl, etc. in the waste gases can be removed by adsorption.
  • the adsorbent capable of decomposing the organic halogen compounds according to the present invention can be used in a low temperature zone at temperatures less than 200° C. in a waste gas-treating system.
  • the most preferable temperature range is approximately 130-150° C. as the waste gas temperature.
  • the way of use is not particularly limited.
  • the adsorbent can be used to treat waste gases, for example, when it is bonded to filter clothes in a bag filter. By so doing, while dust in the waste gases can be filtered off with the bag filter, the organic halogen compounds in the waste gases can also be decomposed with the organic halogen compound-decomposing catalyst. Consequently, SOx, NOx, HCl, etc.
  • the adsorbent having the capability of decomposing the organic halogen compound according to the present invention can simultaneously decompose and adsorb the poisonous components contained in the waste gases.
  • the poisonous components, once adsorbed with the activated carbon, can be gradually decomposed with the organic halogen compound-decomposing catalyst.
  • the useful life of the adsorbent having the capability of decomposing the organic halogen compounds can be largely prolonged as compared with the case where activated carbon is used alone. Thereby, the amount of the secondary waste produced can be suppressed.
  • a catalyst-coating solution was prepared by adding 50 wt. parts of a TiO 2 sol into a dispersion of an organic metal compound precursor which had been synthesized by mixing into 100 wt. parts of an alkoxide derivative of Ti chloroplatinic hexahydrate as a Pt salt in an amount of 1 wt. part as calculated in the form of Pt, and dissolving the resultant mixture into methanol containing 1 wt. part of L-lysine as an amino acid.
  • the samples were set inside a device in which the adsorbents were kept at a temperature of 200° C. and simulated combustion waste gases including orthochlorotoluene were flown.
  • the concentrations of the orthochlorotoluene were measured at inlets and outlets of the adsorbents and in the adsorbents.
  • FIG. 1 is a graph showing orthochlorotoluene adsorption-removing characteristics.
  • FIG. 2 shows the concentrations of orthochlorotoluene in the adsorbents. It is seen from these figures that although the orthochlorotoluene adsorption-removing percentages were as very high (not less than 99%), the organic chlorine compound existed inside the adsorbents carrying no catalyst thereon. However, a large amount of the organic chlorine compound did not remain inside the adsorbent with the catalyst, which revealed that the organic chlorine compound was disposed of
  • the residual amounts of the organic chlorine compound in the used adsorbents can be reduced.
  • the activated carbon can be regenerated at a high temperature of around 500° C. in such a reducing atmosphere that the activated carbon may not be burnt.
  • the higher the temperature in the reducing atmosphere the higher the effectiveness of the Pt/TiO 2 catalyst.
  • the activated carbon carrying Pt/TiO 2 thereon is more readily regenerated.
  • Example 2 orthobromotoluene was used and its absorption-removing characteristics were measured, considering organic bromine compounds including brominated dioxins as other organic halogen compounds, while Example 1 is an example carried out considering the organic chlorine compounds including the dioxins.
  • a catalyst-coating solution was prepared by adding 50 wt. parts of a sol of TiO 2 to an organic metal compound precursor, which had been synthesized by mixing into 100 wt. parts of an alkoxide derivative of Ti chloroplatinic acid hexahydrate as a Pt salt in an amount of 1 wt. part as measured in the form of Pt, and dissolving the resulting mixture into methanol containing 1 wt. part of L-lysine as an amino acid.
  • the samples were set inside a device in which the adsorbents were kept at a temperature of 200° C. and simulated combustion waste gases including an orthobromotoluene were flown.
  • the concentrations of orthobromotoluene were measured at inlets and outlets of the adsorbents and in the adsorbents.
  • FIG. 3 is a graph showing an orthobromotoluene adsorption-removing characteristics.
  • FIG. 4 shows the concentrations of orthobromotoluene in the adsorbents. It is seen from these figures that although the orthobromotoluene adsorption-removing percentages were very high (not less than 99%), the organic bromine compound existed inside the adsorbents carrying no catalyst thereon. However, a large amount of the organic bromine compound did not remain inside the adsorbent with the catalyst, which revealed that the organic bromine compound could be disposed of.
  • Example 3 Pd was used as a catalyst component.
  • a catalyst-coating solution was prepared by adding 50 wt. parts of a sol of TiO 2 to an organic metal compound precursor, which had been synthesized by mixing, into 100 wt. parts of an alkoxide derivative of Ti, palladium nitrate as a Pd salt in an amount of 1 wt. part as measured in the form of Pd, and dissolving the resulting mixture into methanol containing 1 wt. part of L-lysine as an amino acid.
  • What was used in experiments were prepared by impregnating activated carbon with the above catalyst-coating solution and producing an organic halogen compound-decomposing catalyst under heating. Relative to 100 wt. parts of the activated carbon, 1 wt. part of TiO 2 and 0.01 wt. part of Pd were used. For comparison purposes, activated carbons carrying no catalyst thereon were also provided.
  • the concentrations of orthochlorotoluene and that of orthobromotoluene were measured at inlets and outlets of the adsorbents by flowing simulated combustion waste gases containing orthochlorotoluene or orthobromotoluene.
  • FIG. 5 is a graph showing the orgochlorotolune adsorption-removing characteristics.
  • FIG. 6 shows the concentrations of orthochlorotoluene in the adsorbents.
  • FIG. 7 is a graph showing the orthobromotoluene adsorption-removing characteristics.
  • FIG. 8 shows the concentrations of orthobromotoluene in the adsorbents.
  • the adsorbent having the capability of decomposing the organic halogen compound according to the present invention not only adsorbs and decomposes the organic halogen compounds contained in the waste gases, but also can remove heavy metals, SOx, NOx, HCl, etc. by adsorption. Consequently, the adsorbent can prolong its useful life and suppress the amount of a secondary waste produced as compared with a case of activated carbon alone. Further, even if the concentrations of the organic halogen compounds including dioxins, brominated dioxins, etc. at the inlet of the catalyst is low, it is not feared that they are synthesized again.
  • an adsorbent is suitably used for treating the waste gases from incinerators.
  • the processes for producing an organic halogen compound-decomposing catalyst capable of decomposing organic halogen compounds according to the present invention can readily produce the above adsorbent having the capability of decomposing the organic halogen compound.

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KR101278047B1 (ko) 2010-12-20 2013-06-27 대림대학교산학협력단 백금이 분산된 이산화티타늄 전구체의 제조방법
EP2609832A2 (fr) 2002-03-26 2013-07-03 Colgate-Palmolive Company Brosse à dents électrique à sections rotatives

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US6670300B2 (en) * 2001-06-18 2003-12-30 Battelle Memorial Institute Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions
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CN100415367C (zh) * 2005-03-07 2008-09-03 南开大学 纳米金属钯/载体催化剂的制备方法
US20100310441A1 (en) * 2009-06-05 2010-12-09 Basf Corporation Catalytic Article for Removal of Volatile Organic Compounds in Low Temperature Applications
CN102794107A (zh) * 2012-08-31 2012-11-28 中持依迪亚（北京）环境研究所有限公司 一种催化降解二恶英的方法及系统
CN103100386B (zh) * 2013-01-15 2014-08-06 汕头大学 一种用于降解VOCs的整体式催化剂的制备方法
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JP6140326B1 (ja) * 2016-03-08 2017-05-31 株式会社流機エンジニアリング 揮発性有機化合物の吸着剤の再生処理方法
CN108283935A (zh) * 2017-01-09 2018-07-17 青州日新特种材料有限公司 一种NOx脱除催化剂及其制备方法
ES3016664T3 (en) * 2018-12-27 2025-05-09 Nikki Universal Co Ltd Catalyst for ammonia decomposition and exhaust gas treatment method
CN111714964B (zh) * 2020-06-29 2021-08-17 浙江严牌过滤技术股份有限公司 一种除尘脱二噁英一体化滤料及其制备方法
CN113731356A (zh) * 2021-07-07 2021-12-03 生态环境部华南环境科学研究所 一种改性活性炭吸附剂及其制备方法和应用

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KR101278047B1 (ko) 2010-12-20 2013-06-27 대림대학교산학협력단 백금이 분산된 이산화티타늄 전구체의 제조방법

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KR20020040751A (ko) 2002-05-30
JP4834274B2 (ja) 2011-12-14
DE60139313D1 (de) 2009-09-03
EP1287888A4 (fr) 2004-06-16
KR100456600B1 (ko) 2004-11-10
WO2001087478A1 (fr) 2001-11-22
CN1165374C (zh) 2004-09-08
CA2374957C (fr) 2008-07-08
EP1287888B1 (fr) 2009-07-22
CN1380837A (zh) 2002-11-20

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